Vat dyestuffs and process for their formation.



'UERIEIN'GEN-GN-THE-RHINE, GERMANY, ASSIGNQR TU illfcllll a hill do 60. M. B. 151., G3? UEEWIILJ'GEN-UN-THE-RHINE, GERMANY,

Viki'." "'Ilihfifi AND PROCESS FDR THEIR FORMATION.

... WNW-Jami anthraquinone or anthraqiunone derivatives with thiosuliiates.

If for example anthraquinonesulfonic acids or their salts are heated with. thiosulfates, products which can easily be vatted and which take upon cotton in powerful fast tones are formed, while sulfur is liberated.

The products-oi? the process protected by the German Patent black sulfur dyestuffs and they are dyed from sodium. sulfid solution. The products of the present invention are insoluble in sodium sulfid solution, they are dyed from alkaline hydro sulfite vats and they give olive-colored tints. Also the products resultingc; from the process described in German Patel 226879 (Example 3) are not identical with those of the present invention, Apart from the differ ence in color, the dyestuffs prepared according to that specification are all soluble in concentrated sulfuric acid, whereas the new products are insoluble in concentrated sulfuric acid.

For the preparation of sulfur dyestulfs, thiosulfates have heretofore many times been employed, but hitherto always in aqueous solutions and With addition of alkali. The present process on the contrary pr o coeds in the absence of water and alkali, the reacting" mixture remaining dry during the whole process. Such. thiosulfate melts (if melts may in this case be spoken of at all) have not previously been produced. It is surprising that under such circumstances the substances enter into reaction. Comparative experiments have demonstrated that for example a mixture of dry sodium anthraquinone-sulfonate, sulfate "and sulfur does not; react in a similar manner under the same circumstances.

Specification of Letters Eateut.

sublimation of sulfur ceases. powder becomes more and more darkly col Patented li er 2,

Application filed September 15, E913. Serial N 0. 339,879.

Example 1: 100 parts of sodium thraquinonedisulfonate and 400 parts of crystallized sodium thiosulfate are melted together and dried; the dried mass in finely ground form is heated while being stirred in an iron vessel at from 250150 300 C. until the sublimation of sulfur ceases. The powdery mixture, of light-gray color, grad ually assumes a darker olive-green color Without agglomeration. The product can either he vattcd directly for dyeing or after it has been Washed with alkaline water and brought into a paste. The alkaline hydrosulfite vat is deep red-brown, the leucocompound takes upon cotton as a deep black.

l-ifterhanging in the air, rinsing and soap mg, an olive-color of surpassingly fast prop erties results. In the drystate the dyestuff appear as a dark powder which is soluble neither in concentrated sulfuric acid, nor in boiling nitrohenzene nor in boiling cresol.

Example 2; 100 parts of potassium l-anthraquinone' mono sulfonate are ground,

with 300 parts of calcium. thiosulflte and heated in an iron vessel provided'with a stirrer for some hours at 300 to 330 (3., until the The dry ored. After cooling the product is extract ed first with water, then successsively with dilute hydochloric acid and dilute soda lye,

whereupon it can be used directly for dye mg.

acid and in sodium sulfid. The alkaline vat with hydrosulfite is broWn-violet-red. The dyeing upon cotton is Olivegreen.

The properties of the individual dyestuil's are apparent from the table below. The dyeings produced therewith possess in addition to a suliicient fastness to ohlorin an extraon dinary fastness to light, and they are extremely fast to Washing and scalding; the latter property, as is well known, belongs to only few vat-dye-stufi's and it presents in many cases advantages in the Weaving" of the dyed. goods with raw-white and subsequent steeping.

Dyestufi" from potassium 1 anthmgu-inonesulfomte.

It is in concentrated sulfuric acid insoluble.

It is insoluble in concentrated sulfuric Mid It is in sodium suliid solution insoluble. Vat: brown-Violet-red (cold). Dyeing: green-olive.

Dyestufi from sodc'mn 2.6 anthmqmhwnedisulfonote.

It is in concentrated sulfuric acidinsoluble. It is in sodium sulfid solution insoluble. Vat: red-brown (cold).

Dyeing: yellow-olive.

Dg/estufi from potassium Identkmguinona iii clisalfoncte.

It is in concentrated sulfuric acid insol uble. I

It is in sodium sulfid solution insoluble. Vat: violet (cold). Dyeing: grey-olive.

Dyestuf from potassium 1.8-anthragu/in0medisulfanote. It is in concentrated sulfuric acid insoluble. 7

It is in sodium sulfid solution insoluble. i Vat: violet-red (cold). Dyeing: green-olive.

' Dyestu/i' from onthmguinone-eulfonic suits of the German Patent 2023.98 (Ewample It is in concentrated sulfuric acidinsoluble.

It is in sodium sulfid solutioninsoluble.

Vat: brown-red (cold).

Dyeing; brown-olive.

Dyestufl from potassium 1.5-antfi/mgainonedisulfonate, prepared according to the process of the German Patent 226879 (Example 3).

It is in concentrated sulfuric acid soluble with brown coloration.

It is in sodium sulfid solution insoluble.

Vat: brown (only upon heating).

Dlyeing: reddish black-brown.

In addition to their preparation from anthraquinone-sulfonic acid, the new vat-dyestufi's containing sulfur with an-anthraquinone molecule can also he produced by heating dioxy-anthraquinone-sulfonic acids, yiz., v

alizarin-sulfonic acid, anthrafiavic-sulfonic acid, or isoanthraflavic-sulfonic acid with thiosulfates.

If a salt of alizarin-sulfonic acid is first heated with .thiosulfate, the temperature being preferably raised to 330350 C., analogous valuable vat-dyestuifs are formed, the shades of which extend to deep black. The raw product after washing with water and .dilute alkali is suitable for dyeing direct as aste. The dyestufl's are very dark-colored odies and are insoluble in organic solvents sulfon'ate, produced according menses and in concentrated sulfuric acid, also in sodium sulfid. By this property they are sharply distinguished from the products obtained according to the process of the German Patent 95484, which products are dyed from sodium sulfid solution. They are on i the contrary vetted from hydrosulfite in the presence of alkali and "they then take well upon cotton.

' Example 3: 100 parts of ordinary sodium alizarin-sulfonate are added to 500 parts of molten thiosulfate. The whole mass is dehydrated by heating and stirring. The dry powder is then heated in an iron vessel provided with. a stirrer for about six hours at 330335 C. The reaction efiects the elimination of sulfur, which sublimes out from thedry black powder. After cooling the product is washed with water and dilute soda-lye; it then forms a paste with about 70 er cent. of moisture.

' Examp e 4: 100 parts of sodium alizarinto the process of German Patent 210863 are treated as in Example 3.

Example 5: 100 parts of sodium alizarin- 3-sulfonate are mixed with 300 parts of potassium thiosulfate, and then heated while being stirred for two hours at 300 C. and for four hours at 350. The reaction proceeds as described in Example 3.

The method for using the product is also the same.

Dyestufi' from ordinary alz'zaren- -sulfom'o a id Vat: brown-reddish.

Dyeing: black.

Dyestufi' from alz'zarr'm-sulfom'c acids of,

German Patent 210863.

Vat: brown-reddish. Dyeing: black. The dyeingspossess valuable properties of fastness. In addition to a sulhcient fastnessto chlorin, which surpasses considerably that of the products of German Patent 95484, they are notably fast to alkali, to steeping and to light.

Analogous vat-dyestuffs are formed by heating anthraflavic-sulfonic acids or isoanthrirflaviC-sulfonic acids or halogen derivatives of the said 'sulfonic acids with thiosulfates. The dyestuffs obtained in this menses legs are likewise distinguished by a great :Eastness to soap, to inning and to steep mg, they are extraord narily fast to light,

end they considerably exceed in fastness to chiorin even the products prepared from alizarin sulionic acids. lit is surprising that halogen-derivatives of anthraflavic and isoanthrafiavic acids yield upon heating with thiosulfates black vat dyestufi's, Whereas halogen-derivatives of rZ-nzyanthraquinone wheniheated with thiosulfates and subseuentlv chlorinated ve onl oran cred.

shades. l

The method of operation is in all cases the same as that fully described for alizarinsulfonic acids. As sulfo-derivatives there may he used the products sulfonated either direct with fuming sulfuric acid or by addition of horic acid or mercury. As a halogen-derivative the dichloranthraflavic acid obtainable according to the German ill Patent 15217 5 suggests itself on account of its cheapness.

1 stuffs co'ntainin sulfur with an anthraquinone molecule, it is however not necessary to start from the sulfonic acids of an thraquinone'. Many analogous vat-dyestuffs may he obtained also by heating other an thraquincne derivatives, viz. 2-oxyanthraquinone or its halogen-derivatives with thicsulfates. v v

If 1-chlor-2-oxyanthraquinone or dibrom- Q-oxyanthraquinone is first heated with sodium thiosulfate, alkali-insoluble products which dye cotton brown shades from alkaline .vats are first formed. The dyeings are fairly fast to washing and soap. Upon chlorin-ating they gain considerably in purity While the shade changes to orange-red.

The pure orange-red shade can also be produced directly by dissolving the alkali-insoluble raw-product in concentrated sulfuric acid, precipitating the purified dyestufil with water, and then treating the same with alkaline chlorin solution until it has attained the desired purity of shade and chlorin is still only slowly exhausted.

If 1-chlor2-oxyanthraquinone 0r dihronn- EZ-oxyanthraquinone issulojected to the action of alkali sulfids in the presence of water, forcxainple in the process of Ger man Patent 226879, alkali-soluble products The dyestufis produced from anthrafiavic-sulfonio acids can readily be are chiefly formed and the small alkali-insoluble residue is completely destroyed by chlorinating.

Also the pr cess of French Patent all??? leads in the case of l-chlor-cxyanthra quinone or dihrcm-Q-oxyantln'aquinone, to other products, "which are fairly resistant to alkaline chlorination but which are absolutely not fast to acids and alkalis, as the dyeings produced therewith which are beau-- tiii'ul orange upon acidifying become blue red upon the addition of alkali.

Example 7: 10 kilograms of holder-2- oxyanthraquinone are mixed with. kilograms of molten crystallized thiosultate. Thewhole mass is then brought to dryness and powdered. The dry powder is healed to about 200 C. in an iron vesselwith stir rer for about seven hours. At 150 C. the powder begins to darken but it remains powdery durin the whole process. In this case however no sublimation of free sulfur takes place. lifter boiling the mass with hot water, the material not acted upon is extracted with diluted alkali. The alkaliinsoluble product after being dried is dis solved in concentrated sulfuric acid precipitated with water, and in this finely-divided form it istreated with an alkaline chlorin solution until the desired purity oi shade is attained. The product so purified appears, after drying, as a dark brown-red crystalli, .e powder. Its solution in concen trated sulfuric acid is a beautiful green. Water precipitates orange-red flakes therefrom. The solution in-hot nitrobencene is brown. In the former a paste the compound may easily be vetted in the cold with alka line hydrosulfite. From a brown vat cotton is dyed in fast orange-red shades.

vExample 8: By replacing l-chlor-Q-oxyanthraquinone "by dilorom-Q-oxyanthraquinone and otherwise following the method given in Example 7 quite-similar results are arrived at. The purified and dried product appears as a dark hrown-red crystalline powder. From its olive solution in concentrated sulfuric acid, water precipitates brick-red fiakes. The solution in hot nitrohenzene is brown. From alkaline brown vats the dyestufi' dyes cotton in a somewhat more bluish shade than the d estuff in Example 7 does.-

Analogous vat-dyestuffs are obtained if instead of the halogen derivatives or 2- oxyanthraquinone, the latter itself or anthraquinone itself is taken. Anthraquinone or 2oxyanthraquinone is heated with thicsulfates and otherwise treated as described in the foregoing examples for halogen-derivatives of Q-oxyanthraquinone; in this way. quite fast shades are obtained which vary hetween orange and copper shades llil according to the time and the temperature of the reaction.

I claimi 1. Process for producing vat-dyestuffs containing an anthraquinone nucleuscombined with sulfur, which process consists in heating anthraquinone-sulfonic acid with thio-sulfates inthe absence of any solvent or diluent liqui I 2. A product containing an anthraquinone nucleus combined with sulfur, said product memni being obtained by heating anthraquinone suifonic acid with thio-sulfates in the absence of any solvent or diluent liquid.

' In testimony whereof, I have signed my 15 naniejto this specification in the presence of two subscribing witnesses Micnani. innn'enY.

Witnesses:

Josnn Bowman", AUGUSCI Tmnnn. 

